Modified fatty alcohol and process for producing same



- atoms.

become rancid or discolored even upon prolonged V exposure to air orother oxidizing influences and Patented May 14, 1940 PATENT OFFICEMODIFIED FATTY ALCOHOL AND PROCESS FOR PRODUCING SAIWE Edwin A.Robinson, Chatham, N. J., assignor to National Oil Products Company,Harrison, N. J., a corporation of New Jersey Serial No. 267,722

No Drawili'gr Application April 13, 1839, r

20 Claims.

This invention relates to modified fatty alcohols, more particularlyto-blown fatty alcohols having at least 8 carbon atoms.

Unsaturated fatty alcohol compositions having an iodine value aboveabout and comprising an unsaturated alcohol containing at least 8 carbonatoms are readily obtainable from natural products, such as sperm oiland other liquid and solid waxes, castor oil, tease'ed oil and the like.It has been proposed to employ such unsaturated fatty alcoholcompositions as textile lubricants, plasticizers, blending agents andthe like in order to take advantage of their oily or fattycharacteristics and their relatively low vol-' atility. However, thesecompositions tend to become rancid and discolored after contact with airor other oxidizing influences and hence have not been extensivelyemployed for such purposes.

U. S. Patent 2,087,603 describes a process for the production of anagent capable of increasing the oiliness in lubricants which involvesblowing an "alcohol containing at least 10 carbon atoms and having aniodine value below 70, preferably below 20. As above pointed out, thereis a large and readily available supply of unsaturated fatty alcoholcompositions comprising unsaturated alcohols containing at least 8carbon atoms and having iodine values substantially above 70; however,the employment of such compositions in accordance with the process ofthe above patent requires preliminary steps involving hydrogenating thealcohols to reduce the iodine value thereof to substantially below 70and preferably below treating textile materials from unsaturated fattyalcohol compositions having an iodine value substantially above 70, andcomprising an unsaturated alcohol containing at least 8 carbon atoms.

I have now discovered that products of extensive technical importanceand capable of a wide variety of uses may be prepared by blowingunsaturated fatty alcohol compositions having an iodine value aboveabout 70, and comprising an unsaturated alcohol containing at least 8carbon The products of my invention do not hence may be used for mam;purposes for which unblown unsaturated fatty alcohols are unsuitable.They are characterized by iodine values substantially lower than thoseof the unblown alcohol compositions and varying between about 25 andabout 150. The acetyl values of the blown alcohol compositions aregreater than those of the unblown compositions, the increase varyingbetween about 2 and about '75. The viscosities of the unsaturated fattyalcohol compositions generally increase to some extent upon blowing, butthe increase is not as great as the increase in the viscosity of fattyoils on blowing; this factor is .of particular importance in thetreatment of liquid fatty alcohol compositions, since the blown productsremain fluid and may be easily handled, as contrasted with the highlyviscous nature of blown oils.

The unsaturated fatty alcohol compositions which may be treated inaccordance with my invention may comprise any of the unsaturated fattyalcohols containing at least 8 carbon atoms and having an iodine valueabove 70, including alcohols such as oleyl alcohol, ricinoleyl alcohol,linoleyl alcohol, alcohols prepared from oxidized petroleum fractions,wax alcohols, and unsaturated alcohols prepared by the reduction offatty oils or fatty acids such as soybean oil, teaseed oil, oiticia oil,castor oil, olive oil, rice bran oil, fish fatty acids, etc. Theunsaturated fatty alcohol compositions may contain appreciable amountsof saturated alcohols, such as, for example, stearyl alcohol, which maycause the mixture to exist in the form of a paste or a solid. Suchcompositions may also be treated in accordance with my invention,provided their iodine value is substantially above '70, by blowing amolten mass or a solution thereof. Accordingly, the term unsaturatedfatty alcohol compositions when used in the specification and claims isintended to include not only relatively pure unsaturated fatty alcoholscontaining at least 8 carbon atoms, but also mixtures of theseunsaturated fatty alcohols including those containing appreciableamounts of saturated fatty alcohols. Likewise, the term "blown fattyalcohol compositions is intended to cover compositions produced byblowing the unsaturated fatty alcohol compositions.

The blown fatty alcohol compositions of my invention may be prepared bycontacting an unsaturated fatty alcohol composition comprising analcohol having at least 8 carbon atoms and having an iodine value aboveabout '10 with air, oxygen, ozone. or mixtures thereof. The

troleum solvents such assolvent naphtha, xylene or'isopropyl alcohol; orthe fatty alcohol composition may be sprayed through a body of any ofthe above oxidizing agents. Any other suitable method of contact may beused. The blowing treatment may be carried out in the presence ofcatalysts such as, for example, metallic driers,

peroxides, etc., to accelerate the reaction. The

unsaturated fatty alcohol compositions may advantageously be mixed priorto blowing with a relatively small amount of water, e. g. about 10%,since I have found that the hydroxyl content and the surface activity ofthe blown alcohols are thereby substantially increased. The time ofblowing may vary widely depending upon the characteristics desired inthe final product; generally, however, between about 3 and about 36hours are suitable. The blowing may be conducted at any desiredtemperature, but elevated temperatures, for example, between about 75and about 200 C., are preferred.

The blown alcohol compositions obtained in accordance with the aboveprocess may be in liquid or solid form depending upon whether a liquidor solid fatty alcohol composition is treated.

The exact constitution of. the blown product is somewhat uncertain, butthe product still displays alcoholic properties indicating the alcoholichydroxyl 'group remains unaltered. The product 'has an iodine valuesubstantially lower than that of the original alcohols, and whichmayvary between about 25 and about 150, preferably between about 40 andabout 80 depending somewhat upon the conditions of blowing. The acetylvalue of the alcohols increasessubstantially on blowing. the increasedepending upon the conditions of blowing, particularly on whether wateris mixed with the composition being blown, and varying between about 2and about '75, preferably between about 4 and about 35. The color of theblown product may range from light amber to black depending somewhatupon the source of the unsaturated fatty alcohol composition treated.The light-colored product's ordinarily need no further processing; theyare either clear amber liquids or solids and have a pleasant odor and acharacteristic oily feel. If the blown product posesses an undesirabledark color, this may be removed bydistilling the product and recoveringa light-colored blown alcohol composition from the distillate; ifdesired, the distillate maybe treated with a bisulphite, such as sodiumbisulphite, whereby impurities of a ketonic and aldehydic nature areremoved The light-colored distillate thus recovered resembles thelightcolored -products above described and may be used as desired.

The following examples are illustrative of my.

invention. Amounts are given in parts by weight.

EXAMPLE I '100 parts of oleyl alcohol having an iodine value of 87.6, anacetyl value of 1'77, and a viscosity of 110 at 38 C. were blown withair for T2 hours at a temperature of 140 C. A clear, amber, oily liquidwas thereby obtained which had an iodine value of 76.1, an acetyl valueof 181, and a viscosity of 205 at 38 C. This liquid did hotbecome rancideven upon exposure to air for several weeks.

' inc.

EXAMPLE II 100 parts of a mixture of fatty alcohols obtained byextracting saponified sperm oil with ethylene dichloride having aniodine value of 78.3, and an acetyl value of 192 were blown with air for12 hours at 140 C. A dark-colored,'oily product was thereby obtainedwhich had an iodine value of 45, and an acetyl value of 211.3.-

This product was vacuum-distilled, using a water pump, and a clear,oily, amber-colored distillate recovered; the distillate comprised amixture of alcohols and had an iodine value of 58 and an acetyl valve of226. A black tarry residue left in the still was discarded.

The blown fatty alcohol compositions produced. in accordancewith myinvention have been found: to be particularly useful for finishing andlubricating textiles because of their oily characteristics and theirproperty of remaining on the surface of textiles, such as cotton, wool,silk and rayon, after contacttherewith. These compositions also act.

as d'e-electrifying agents when contacted with the textiles. Thus theblown alcohol compositions may be employed in compositions used forfinishotherwise conditioning textiles, such as wool, silk, cotton orrayon in accordance with methods well known in the art. The followingrepresent examples illustrating particular compositions fir positions ofmy invention may be employed.

A. Finishing oil for silk, rayon, piece goods, knitwear An aqueousemulsion was prepared containing 1 tov 2% of a composition comprising 50parts of the sulfonated isobutyl ester of sperm oil, 25 parts coconutoil, and 25 parts of blown alcohols obtained by blowing alcoholsresulting from the reduction of teaseed oil. This emulsion was appliedon a quetsch to a silk fabric followed by tenter frame drying. It wasfound the emulsion imparted to the fabric excellent softness and drape.

The above example was also carriedout employing rayon fabric or knitgoods, and the results were found to be equally desirable.

B. Silk soaking oil produced silk capable of being plied and thrown andthen subsequently knit into a full-fashioned hose.

C. Wool lubricant A composition comprising 10 parts of blown sperm oilalcohols, 10 parts of sulfated teaseed oil, and 50 parts of paraflin oil.was prepared.

. This composition was applied straight to the lubricating, lustering,soaking, sizing 0rextent of 4% to wool fibers during the batching 1).Yar'n lubricant A composition comprising parts glyceryl mono-oleate, 50parts blown ricinoleyl alcohol,

treating textiles in which the blown alcohol comat least 8 carbon atomsand having an iodine 10 parts olive oil, and 10 parts isopropyl alcoholwas prepared. The composition was emulsified in water and used in thelast rinse on mercerized cotton yarns. Such yarns were capable of beingknit so as to produce knit wear with a minimum number of courses perinch.

In addition -to their employment as textile treating agents, the blownfatty alcohol compositions produced in" accordance with my invention mayalso be employed in a variety of other manners; thus they may be used asplasticizers and defoamers for adhesives such as glue and casein;

' as auxiliary emulsifiers, blending aids and softeners in cosmetics; aspour point depressants in fuels and lubricants; as surface tensionaltering agents in insecticidal sprays; as dispersing, plasticizing andthickening agents for inks; in fat liquoring, waterproofing andsoftening of leather; as agents to increase the oiliness and to act assludge dispersers in lubricants; as plasticizers and softeners inpaints, varnishes, lacquers and resins; as dispersing agents in paperfillers; as demulsifiers for crude oil emulsions; in polishes and waxesfor automobiles, shoes, floors, etc.; as oil-soluble dye dispersers; andas emulsifying and stabilizing aids in latex compositions. The blownalcohols may be reacted with inorganic acids, such as sulfuric acid andphosphoric acid, or derivatives thereof to produce inorganic neutral oracid esters having valuable properties; for example, the sulfates andphosphates of the blown alcohols possess excellent wetting anddispersing properties. The blown alcohols may also be condensed in anysuitable manner with aromatic compounds, such as benzene, toluene,naphthalene, phenols and naphthols. and the condensation products thentreated with sulfuric acid to give valuable wetting and dispersingagents. In addition to the above uses, it will be evident to thoseskilled in the art, in view of the properties that they may be used formany additional purposes to great advantage.

Since certain changes may be made in the above products and differentembodiments of the invention could be made without departing from thescope thereof, it is intended that all matter contained in the abovedescription shall be interpreted asillustrative and not in a limitingsense.

Having described my invention, what I claim as new and desire to secureby Letters Patent is:

l. A blown fatty alcohol composition having an iodine value betweenabout 25 and about 150, and an acetyl value greater than that of thecorresponding unsaturated fatty alcohol composition by an amount betweenabout 2 and about 75.

2. A blown fatty alcohol composition having an iodine value betweenabout 25 and about 150, an acetyl value greater than that of thecorrespond ing unsaturated fatty alcohol composition by an amountbetween about 2 and about 75, and comprising an alcohol having at least8 carbon atoms, said composition being obtainable by blowing anunsaturated fatty alcohol composition having an iodine value above about70 and containing an unsaturated alcohol having at least 8 carbon atoms.

3. A composition for treating textiles comprising a blown fatty alcoholcontaining at least 8 carbon atoms-and having an iodine value betweenabout 40 and about 80, and an acetyl value greater than that of thecorresponding unsaturated fatty alcohol by an amount between about 4 andabout 35, said alcohol being obtainable by blowing an unsaturated fattyalcohol containing value above about 70.

4. A composition for treating textiles comprising a blown fatty alcoholcomposition having an iodine value between about 40 and about 80, anacetyl value greater than that of the corresponding unsaturated fattyalcohol composition by an amount between about 4 and about 35, andcomprising an alcohol having at least 8 carbon atoms and an appreciableamount of a substantially saturated fatty alcohol, said compositionbeing obtainable by blowing an unsaturated fatty alcohol compositionhaving an iodine value above about 70 and containing an'unsaturatedalcohol having at least 8 carbon atoms and appreciable amounts of asubstantially saturated fatty alcohol. r

5. Blown oleyl alcohol having an iodine value between about 40 and about80, and an acetyl value greater than that of the oleyl alcohol by anamount between about 4 and about 35.

6. Blown sperm oil alcohols having an iodine value between about 40 andabout 80, and an acetyl value greater than that of the sperm oilalcohols by an amount between about 4 and about 35.

7. Blown ricinoleyl alcohol having an iodine value between about 40 andabout 80, and an acetyl value greater than that of the ricinoleylalcohol by an amount between about 4 and about 35.

8. A process for preparing blown fatty alcohol compositions whichcomprises contacting an unsaturated fatty alcohol composition having aniodine value above about 70 with an oxidizing agent selected from thegroup consisting of air, oxygen, ozone, and mixtures thereof.

9. A process for preparing blown fatty alcohol compositions whichcomprises contacting an unsaturated fatty alcohol composition having aniodine value above about 70 and containing an unsaturated alcohol havingat least 8 carbon atoms with an oxidizing agent selected from the groupconsisting of air, oxygen, ozone, and mixtures thereof at an elevatedtemperature.

10. A process for preparing blown fatty alcohol compositions fortreating textiles which comprises contacting an unsaturated fattyalcohol composition having an iodine value above about .70 andcontaining an unsaturated alcohol having at least 8 carbon atoms withair at a temperature between about 75 and about 200 C. and for a timebetween about 3 and about 36 hours, distilling the blown product andrecovering the desired product from the distillate.

11. A process for preparing blown fatty alcohol compositions fortreating textiles which comprises contacting an unsaturated fattyalcohol composition having an iodine value above about 70 and containingan unsaturated alcohol having at least 8 carbon atoms with an oxidizingagent selected from the group consisting of air, oxygen, ozone andmixtures thereof in the presence of a relatively small amount of water.

12. A process for preparing blown fatty alcohol compositions whichcomprises blowing oleyl alcohol for between about 3 and about 36 hoursat a temperature between about 75 and about 200 C.

13. A process for preparing blown fatty alcohol compositions whichcomprises blowing sperm oil alcohols for between about 3 and about 36hours at a temperature between about 75 and about 200 C.

14. A process for preparing blown fatty alcohol compositions whichcomprises blowing ricinoleyl alcohol for ,between about 3 and about 36hours at a temperature between about 75 and about 200 C.

15. A process of treating textileswhich comprises treating a textilematerial with anagent comprising a blown fatty alcohol compositionhaving an iodine value between about 25 and about 150, and an acetylvalue greater than that of the corresponding unsaturated fatty alcoholcomposition by an amount between about 2 and about 75. I

16. A process of treating textiles which com prises treating a textilematerial with an agent comprising a blown fatty alcohol composition'having an iodine value between about 25 and aboutl50, and an acetylvalue greater than that of the corresponding unsaturated fatty alcohol'compositionby an amount between about 2 and about 75, and comprising analcohol having at least 8 carbon atoms, said blown fatty alcoholcomposition being obtainable by blowing an unsaturated fatty alcoholcomposition having an iodine value above about '70 and containing anunsaturated alcohol having at least 8 carbon atoms.

1'7. A process of treating textiles which comprises contacting a textilematerial with an agent comprising a blown fatty alcohol compositionhaving an iodine value between about 40 and about 80, and an acetylvalue greater than that of the corresponding unsaturated fatty alcoholcomposition by an amount between about 4 and about 35, and comprising analcohol having at least 8 carbon atoms, said blown fatty alcoholcomposition being obtainable by blowing an unsaturated fatty alcoholcomposition having an iodine value above about '10 and containing anatoms. 1 t

18. A process of treating textiles which comprises contacting a textilematerial with an agent comprising blown oleyl alcohol having an iodinevalue between about 40 and about 80, and an acetyl value greater thanthat of oleyl alcohol by an amount between about 4 and about 35.

19. A process of treating textiles which comprises contacting a textilematerial with an agent comprising blown sperm oil alcohols having aniodine value between about 40 and about 80, and an acetyl value greaterthan that of the sperm oil alcohols by an amount between about 4 andabout 35.

20. A process of treating textiles which comprises contacting a textilematerial with an agent comprising blown ricinoleyl alcohol havingunsaturated alcohol having at least 8 carbon an iodine value betweenabout 40 and about 80,

and an acetyl value greater than that of ricinoleyl alcohol by an amountbetween about 4 and about 35.

EDW'IN A. ROBINSON.

